Final Report: SOA Volatility Evolution: Formation and Oxidation over the Lifecycle of PM2.5

EPA Grant Number: R833746
Title: SOA Volatility Evolution: Formation and Oxidation over the Lifecycle of PM2.5
Investigators: Donahue, Neil , Kroll, Jesse H. , Pandis, Spyros N. , Worsnop, Douglas R.
Institution: Carnegie Mellon University , Aerodyne Research Inc.
EPA Project Officer: Chung, Serena
Project Period: September 1, 2007 through August 31, 2011
Project Amount: $599,990
RFA: Sources and Atmospheric Formation of Organic Particulate Matter (2007) RFA Text |  Recipients Lists
Research Category: Air Quality and Air Toxics , Particulate Matter , Air

Objective:

The objective of this project was to identify the major mechanisms for the aging of organic particulate matter in the atmosphere and to implement accurate parameterizations of those findings in air quality models. In so doing, we strove to understand the relative contribution of human activity and natural emissions to organic aerosol levels and to enable and inform policy actions aimed at organic-aerosol reductions.

Summary/Accomplishments (Outputs/Outcomes):

A notable experimental undertaking for 2008 was an intensive series of experiments in July 2008 involving the High-resolution Aerosol Mass Spectrometer operated by co-investigator Jesse Kroll at Carnegie Mellon University (CMU) for 3 weeks. We examined the interaction of anthropogenic and biogenic secondary organic aerosol (SOA) by using an isotopic label on toluene (a major source of anthropogenic SOA) to separate it from α-pinene SOA, generating first one and then the other SOA by oxidation of each precursor, and then observing the mixing behavior with high-resolution mass spectrometry.

During the remainder of the year, we separately investigated SOA formation from toluene, and α-pinene. We found significantly higher SOA yields than previous observations (confirming a recent finding from Caltech for low-NOx conditions and extending it to high-NOx conditions). This was published in Atmosperhic Chemistry and Physics. For α-pinene, we examined the volatility of SOA using thermodenuder measurements and also the influence of aging by exposure to OH radicals. Again, this showed significant changes in SOA concentrations, with an effect that appears to depend dramatically on the presence of UV light.

The aging of α-pinene SOA became the centerpiece of a multiple chamber experiment conducted by the principal investigator (PI) as part of his sabbatical research during 2008-2009. This research included the STAR-supported chamber experiments at CMU and parallel experiments at the Paul Scherrer Institute in Switzerland and Forschungszentrums in Karlsruhe and Juelich, Germany. Using different chambers with different radical sources, different wall characteristics, and different volume to area ratios we were able to probe the dramatic consequences. The bottom line is that SOA from this important biogenic source can easily double or even triple after aging by OH radicals equivalent to roughly 1 day of exposure, but the aging shows signs of being quite sensitive to photochemistry. This project led to nine publications (see publications list) and has spawned several subsequent research proposals. Implementations of aging mechanisms in our 2D volatility basis set (VBS) are consistent with the chamber experiments, showing a very sharp enhancement in SOA levels after OH oxidation.

Parallel work in the CMU smog chamber has revealed that SOA formed under low-NOx conditions is highly vulnerable to photolysis. Consequently, one reason that SOA levels appear to be correlated with urban activity, even though biogenic carbon appears to frequently dominate the carbon sources, could be a dependence in the LOSS of SOA on the production pathway, with high-NOx SOA being less vulnerable to photodegradation than low-NOx SOA.

We have implemented the volatility basis set developed under our previous STAR grant in the air-quality model PMCAMx and investigated the effect of these aging reactions on SOA levels. The upshot is that increased SOA formation from toluene oxidation substantially improves model-measurement agreement, while enhanced SOA from α-pinene SOA aging is inconsistent with organic aerosol measurements in the southeastern United States. The model disagreement with α-pinene aging in the 1D-VBS used in this model may well be alleviated with the 2D-VBS aging mechanism that now is constrained by chamber observations from this STAR project.

Two papers in Geophysical Research Letters provide substantial constraints on the thermodynamics associated with organic-aerosol phase partitioning. One by Noenne Prisle (visiting doctoral student from Copenhagen) shows that we can observe a mild enhancement in SOA formed on dry inorganic seed particles as humidity increases only after those seeds deliquesce, but that the SOA and the inorganic phases remain largely separate. A second complementary study supported under STAR Grant R833748 showed that mixing among different organic aerosol types (SOA and POA) is quite sensitive to the composition of the organics, but that complex mixtures such as actual diesel emissions appear to mix with SOA, while less complex mixtures (such as pure oil) do not. This has significant implications to OA mixing assumptions used in chemical transport models.

We made extensive use of isotopic labeling along with our high-resolution aerosol mass spectrometer to address the thermodynamics of mixing of different SOA types. Specifically, we showed that SOA formed from a biogenic precursor (α-pinene) and SOA formed from an anthropogenic precursor (toluene) do mix and enhance each other's mass yields consistent with ideal solution theory. This confirms both that the equilibrium mixing theory used for the past 20 years to treat SOA thermodynamics is appropriate and also that these laboratory systems reach equilibrium relative quickly (within a few hours on the outside).

Finally, we have made extensive progress developing a 2D version of our volatility basis set (incorporating the degree of oxidation of organics as a second axis) and implementing the 2D-VBS in a Lagrangian parcel-following version of the chemical transport model PMCAMx. This new model has been used to examine the extensive regional oxidation observed during a continent-scale measurement program in Europe (EUCAARI). The model successfully reproduces both the levels and diurnal behavior of organic aerosol as well as the very high degree of oxidation observed at remote sites and the intermediate degree of oxidation seen at more regional sites.

Conclusions:

In summary, we have significantly advanced our understanding of SOA sources through a series of experiments on SOA formation, mixing, and aging. We have implemented these findings in chemical transport models and shown that the model predictions are consistent with field data. Thus, the findings of this project are ready for use in policy decision making.


Journal Articles on this Report : 29 Displayed | Download in RIS Format

Other project views: All 68 publications 31 publications in selected types All 31 journal articles
Type Citation Project Document Sources
Journal Article Barmet P, Dommen J, DeCarlo PF, Tritscher T, Praplan AP, Platt SM, Prevot ASH, Donahue NM, Baltensperger U. OH clock determination by proton transfer reaction mass spectrometry at an environmental chamber. Atmospheric Measurement Techniques 2012;5(3):647-656. R833746 (Final)
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  • Journal Article Bothe M, Donahue NM. Organic aerosol formation in citronella candle plumes. Air Quality, Atmosphere and Health 2010;3(3):131-137. R833746 (2009)
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  • Journal Article Chacon-Madrid HJ, Presto AA, Donahue NM. Functionalization vs. fragmentation: n-aldehyde oxidation mechanisms and secondary organic aerosol formation. Physical Chemistry Chemical Physics 2010;12(42):13975-13982. R833746 (2009)
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  • Journal Article Chacon-Madrid HJ, Donahue NM. Fragmentation vs. functionalization:chemical aging and organic aerosol formation. Atmospheric Chemistry and Physics 2011;11(20):10553-10563. R833746 (Final)
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  • Journal Article Chen Q, Liu Y, Donahue NM, Shilling JE, Martin ST. Particle-phase chemistry of secondary organic material: modeled compared to measured O:C and H:C elemental ratios provide constraints. Environmental Science & Technology 2011;45(11):4763-4770. R833746 (Final)
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  • Journal Article Donahue NM, Robinson AL, Pandis SN. Atmospheric organic particulate matter: from smoke to secondary organic aerosol. Atmospheric Environment 2009;43(1):94-106. R833746 (2008)
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  • Journal Article Donahue NM, Epstein SA, Pandis SN, Robinson AL. A two-dimensional volatility basis set: 1. Organic-aerosol mixing thermodynamics. Atmospheric Chemistry and Physics 2011;11(7):3303-3318. R833746 (Final)
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  • Journal Article Donahue NM, Henry KM, Mentel TF, Kiendler-Scharr A, Spindler C, Bohn B, Brauers T, Dorn HP, Fuchs H, Tillmann R, Wahner A, Saathoff H, Naumann KH, Mohler O, Leisner T, Muller L, Reinnig MC, Hoffmann T, Salo K, Hallquist M, Frosch M, Bilde M, Tritscher T, Barmet P, Praplan AP, DeCarlo PF, Dommen J, Prevot AS, Baltensperger U. Aging of biogenic secondary organic aerosol via gas-phase OH radical reactions. Proceedings of the National Academy of Sciences of the United States of America 2012;109(34):13503-13508. R833746 (Final)
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  • Journal Article Donahue NM, Kroll JH, Pandis SN, Robinson AL. A two-dimensional volatility basis set – Part 2: Diagnostics of organic-aerosol evolution. Atmospheric Chemistry and Physics 2012;12(2):615-634. R833746 (Final)
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  • Journal Article Frosch M, Bilde M, DeCarlo PF, Juranyi Z, Tritscher T, Dommen J, Donahue NM, Gysel M, Weingartner E, Baltensperger U. Relating cloud condensation nuclei activity and oxidation level of α-pinene secondary organic aerosols. Journal of Geophysical Research:Atmospheres 2011;116(D22):D22212 (9 pp.). R833746 (Final)
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  • Journal Article Hallquist M, Wenger JC, Baltensperger U, Rudich Y, Simpson D, Claeys M, Dommen J, Donahue NM, George C, Goldstein AH, Hamilton JF, Herrmann H, Hoffmann T, Iinuma Y, Jang M, Jenkin ME, Jimenez JL, Kiendler-Scharr A, Maenhaut W, McFiggans G, Mentel TF, Monod A, Prevot ASH, Seinfeld JH, Surratt JD, Szmigielski R, Wildt J. The formation, properties and impact of secondary organic aerosol:current and emerging issues. Atmospheric Chemistry and Physics 2009;9(14):5155-5236. R833746 (2008)
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  • Journal Article Henry KM, Donahue NM. Effect of the OH radical scavenger hydrogen peroxide on secondary organic aerosol formation from α-pinene ozonolysis. Aerosol Science and Technology 2011;45(6):696-700. R833746 (Final)
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  • Journal Article Henry KM, Donahue NM. Photochemical aging of α-pinene secondary organic aerosol: effects of OH radical sources and photolysis. Journal of Physical Chemistry A 2012;116(24):5932-5940. R833746 (Final)
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  • Journal Article Henry KM, Lohaus T, Donahue NM. Organic aerosol yields from α-pinene oxidation: bridging the gap between first-generation yields and aging chemistry. Environmental Science & Technology 2012;46(22):12347-12354. R833746 (Final)
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  • Journal Article Hildebrandt L, Donahue NM, Pandis SN. High formation of secondary organic aerosol from the photo-oxidation of toluene. Atmospheric Chemistry and Physics 2009;9(9):2973-2986. R833746 (2009)
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  • Journal Article Hildebrandt L, Henry KM, Kroll JH, Worsnop DR, Pandis SN, Donahue NM. Evaluating the mixing of organic aerosol components using high-resolution aerosol mass spectrometry. Environmental Science & Technology 2011;45(15):6329-6335. R833746 (Final)
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  • Journal Article Hoyle CR, Boy M, Donahue NM, Fry JL, Glasius M, Guenther A, Hallar AG, Huff Hartz K, Petters MD, Petaja T, Rosenoern T, Sullivan AP. A review of the anthropogenic influence on biogenic secondary organic aerosol. Atmospheric Chemistry and Physics 2011;11(1):321-343. R833746 (Final)
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  • Journal Article Jimenez JL, Canagaratna MR, Donahue NM, Prevot AS, Zhang Q, Kroll JH, DeCarlo PF, Allan JD, Coe H, Ng NL, Aiken AC, Docherty KS, Ulbrich IM, Grieshop AP, Robinson AL, Duplissy J, Smith JD, Wilson KR, Lanz VA, Hueglin C, Sun YL, Tian J, Laaksonen A, Raatikainen T, Rautiainen J, Vaattovaara P, Ehn M, Kulmala M, Tomlinson JM, Collins DR, Cubison MJ, Dunlea EJ, Huffman JA, Onasch TB, Alfarra MR, Williams PI, Bower K, Kondo Y, Schneider J, Drewnick F, Borrmann S, Weimer S, Demerjian K, Salcedo D, Cottrell L, Griffin R, Takami A, Miyoshi T, Hatakeyama S, Shimono A, Sun JY, Zhang YM, Dzepina K, Kimmel JR, Sueper D, Jayne JT, Herndon SC, Trimborn AM, Williams LR, Wood EC, Middlebrook AM, Kolb CE, Baltensperger U, Worsnop DR. Evolution of organic aerosols in the atmosphere. Science 2009;326(5959):1525-1529. R833746 (2009)
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  • Journal Article Kroll JH, Donahue NM, Jimenez JL, Kessler SH, Canagaratna MR, Wilson KR, Altieri KE, Mazzoleni LR, Wozniak AS, Bluhm H, Mysak ER, Smith JD, Kolb CE, Worsnop DR. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol. Nature Chemistry 2011;3(2):133-139. R833746 (Final)
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  • Journal Article Lee B-H, Pierce JR, Engelhart GJ, Pandis SN. Volatility of secondary organic aerosol from the ozonolysis of monoterpenes. Atmospheric Environment 2011;45(14):2443-2452. R833746 (2008)
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  • Journal Article Maksymiuk CS, Gayahtri C, Gil RR, Donahue NM. Secondary organic aerosol formation from multiphase oxidation of limonene by ozone: mechanistic constraints via two-dimensional heteronuclear NMR spectroscopy. Physical Chemistry Chemical Physics 2009;11(36):7810-7818. R833746 (2009)
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  • Journal Article Muller L, Reinnig M-C, Naumann KH, Saathoff H, Mentel TF, Donahue NM, Hoffmann T. Formation of 3-methyl-1,2,3-butanetricarboxylic acid via gas phase oxidation of pinonic acid – a mass spectrometric study of SOA aging. Atmospheric Chemistry and Physics 2012;12(3):1483-1496. R833746 (Final)
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  • Journal Article Murphy BN, Pandis SN. Simulating the formation of semivolatile primary and secondary organic aerosol in a regional chemical transport model. Environmental Science & Technology 2009;43(13):4722-4728. R833746 (2008)
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  • Journal Article Murphy BN, Pandis SN. Exploring summertime organic aerosol formation in the eastern United States using a regional-scale budget approach and ambient measurements. Journal of Geophysical Research–Atmospheres 2010;115(D24):D24216 (12 pp.). R833746 (Final)
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  • Journal Article Murphy BN, Donahue NM, Fountoukis C, Pandis SN. Simulating the oxygen content of ambient organic aerosol with the 2D volatility basis set. Atmospheric Chemistry and Physics 2011;11(15):7859-7873. R833746 (Final)
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  • Journal Article Prisle NL, Engelhart GJ, Bilde M, Donahue NM. Humidity influence on gas-particle phase partitioning of α-pinene + O3 secondary organic aerosol. Geophysical Research Letters 2010;37(1):L01802 (5 pp.). R833746 (2009)
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  • Journal Article Riipinen I, Pierce JR, Yli-Juuti T, Nieminen T, Hakkinen S, Ehn M, Junninen H, Lehtipalo K, Petaja T, Slowik J, Chang R, Shantz NC, Abbatt J, Leaitch WR, Kerminen V-M, Worsnop DR, Pandis SN, Donahue NM, Kulmala M. Organic condensation: a vital link connecting aerosol formation to cloud condensation nuclei (CCN) concentrations. Atmospheric Chemistry and Physics 2011;11(8):3865-3878. R833746 (Final)
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  • Journal Article Salo K, Hallquist M, Jonsson AM, Saathoff H, Naumann K-H, Spindler C, Tillmann R, Fuchs H, Bohn B, Rubach F, Mentel TF, Muller L, Reinnig M, Hoffmann T, Donahue NM. Volatility of secondary organic aerosol during OH radical induced ageing. Atmospheric Chemistry and Physics 2011;11(21):11055-11067. R833746 (Final)
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  • Journal Article Tritscher T, Dommen J, DeCarlo PF, Gysel M, Barmet PB, Praplan AP, Weingartner E, Prevot ASH, Riipinen I, Donahue NM, Baltensperger U. Volatility and hygroscopicity of aging secondary organic aerosol in a smog chamber. Atmospheric Chemistry and Physics 2011;11(22):11477-11496. R833746 (Final)
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  • Supplemental Keywords:

    air quality modeling, smog, particulate matter, organics

    Relevant Websites:

    CAPS - Center for Atmospheric Particle Studies | Carnegie Mellon University Exit

    Progress and Final Reports:

    Original Abstract
  • 2008 Progress Report
  • 2009 Progress Report
  • 2010 Progress Report